Unifying the 2e– and 4e– Reduction of Oxygen on Metal Surfaces

Venkatasubramanian Viswanathan; Heine Anton Hansen; Jan Rossmeisl; Jens K. Nørskov

doi:10.1021/jz301476w

Unifying the 2e^–and 4e^– Reduction of Oxygen on Metal Surfaces

Venkatasubramanian Viswanathan, Heine Anton Hansen, Jan Rossmeisl, Jens K. Nørskov

Research output: Contribution to journal › Journal article › Research › peer-review

290 Downloads (Pure)

Abstract

Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e^–versus 4e^– reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔG_OH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e^– and 4e^– reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e^– reduction, this weak binding is optimal for the 2e^– reduction to H₂O₂. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.

Original language	English
Journal	The Journal of Physical Chemistry Letters
Volume	3
Issue number	20
Pages (from-to)	2948-2951
ISSN	1948-7185
DOIs	https://doi.org/10.1021/jz301476w
Publication status	Published - 2012

Bibliographical note

© 2012 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Keywords

selectivity
activity volcano
electrocatalysis
fuel cells
hydrogen peroxide
lithium-air batteries

Access to Document

10.1021/jz301476w

Jz301476wFinal published version, 225 KB

Cite this

@article{119e9b52f5b5404e8f6b8928fb348f61,

title = "Unifying the 2e– and 4e– Reduction of Oxygen on Metal Surfaces",

abstract = "Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e– versus 4e– reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔGOH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e– and 4e– reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e– reduction, this weak binding is optimal for the 2e– reduction to H2O2. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.",

keywords = "selectivity, activity volcano, electrocatalysis, fuel cells, hydrogen peroxide, lithium-air batteries",

author = "Venkatasubramanian Viswanathan and Hansen, {Heine Anton} and Jan Rossmeisl and N{\o}rskov, {Jens K.}",

note = "{\textcopyright} 2012 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.",

year = "2012",

doi = "10.1021/jz301476w",

language = "English",

volume = "3",

pages = "2948--2951",

journal = "The Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society",

number = "20",

}

TY - JOUR

T1 - Unifying the 2e– and 4e– Reduction of Oxygen on Metal Surfaces

AU - Viswanathan, Venkatasubramanian

AU - Hansen, Heine Anton

AU - Rossmeisl, Jan

AU - Nørskov, Jens K.

N1 - © 2012 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

PY - 2012

Y1 - 2012

N2 - Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e– versus 4e– reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔGOH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e– and 4e– reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e– reduction, this weak binding is optimal for the 2e– reduction to H2O2. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.

AB - Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e– versus 4e– reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔGOH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e– and 4e– reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e– reduction, this weak binding is optimal for the 2e– reduction to H2O2. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.

KW - selectivity

KW - activity volcano

KW - electrocatalysis

KW - fuel cells

KW - hydrogen peroxide

KW - lithium-air batteries

U2 - 10.1021/jz301476w

DO - 10.1021/jz301476w

M3 - Journal article

VL - 3

SP - 2948

EP - 2951

JO - The Journal of Physical Chemistry Letters

JF - The Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 20

ER -